Liquid copolymers of vinyl monomers and unsaturated diesters

ABSTRACT

There is disclosed the preparation of flexible or rigid polyurethane foams of improved physical and chemical properties by the chemical reaction of (A) an organic polyisocyanate and (B) the copolymer of (a) a polymerizable organic vinyl monomer having either one double bond or two double bonds in conjugation to each other and (b) a hydroxyl-containing comonomer consisting essentially of an unsaturated polyalkylene ether macromonomer which has an equivalent weight of about 100 to 3000 and which contains one to three hydroxyl groups and one copolymerizable unsaturation per molecule.

United States Patent [1 1 Fabris et a1.

[ Nov. 4, 1975 both of Akron; Edwin M. Maxey, Kent, all of Ohio [73] Assignee: The General Tire & Rubber Company, Akron, Ohio [22] Filed: Apr. 5, 1974 [21] Appl. No.: 458,301

Related US. Application Data [62] Division of Ser. No. 309,234, Nov. 24, 1972, Pat. No.

I [52] US. Cl. 260/465.4; 260/294.9; 260/295;

260/464; 260/465 D; 260/468 G; 260/471 R; 260/475 P; 260/482 R; 260/485 G; 260/486 B [51] Int. Cl. C07C 69/34; C07C 69/76; C07C 121/28 [58] Field of Search 260/465.4, 485 G, 486 B, 260/475 P [56] References Cited UNITED STATES PATENTS 3,356,637 12/1967 Slocombe 260/785 CL X 3,360,545 12/1967 Wygarlt 260/485 X 3,652,639 3/1972 Pizzini et all 260/465.4 3,654,224 4/1972 Milgrom 260/475 P Primary ExaminerLewis Gotts Assistant Examiner-Dolph l-l. Torrence 7] ABSTRACT There is disclosed the preparation of flexible or rigid polyurethane foams of improved physical and chemical properties by the chemical reaction of (A) an organic polyisocyanate and (B) the copolymer of (a) a polymerizable organic vinyl monomer having either one double bond or two double bonds in conjugation to each other and (b) a hydroxyl-containing comonomer consisting essentially of an unsaturated polyalkylene ether macromonomer which has an equivalent weight of about 100 to 3000 and which contains one to three hydroxyl groups and one copolymerizable unsaturation per molecule.

8 Claims, No Drawings LIQUID COPOLYMERS OF VINYL MONOMERS AND UNSATURATED DIESTERS This is a division of application Ser. No. 309,234, filed Nov. 24, 1972, now U.S. Pat. No. 3,850,861.

BACKGROUND OF THE INVENTION Polyurethanes have been defined as those polymers containing the characteristic urethane linkage,

which can be considered a mixed amide ester of carbonic acid. The urethane polymers" comprise not only homopolymers, but also copolymers wherein the urethane may be only one of many types of linkages in the polymer chain. Thus, a polyurethane may also be comprised of a wide variety of radicals and linkages including oxygen, sulfur, nitrogen, and carbon-containing groups such as amino, amido, sulfoamido, ester, ether, and hydrocarbon radicals and linkages.

It is well known that a polyurethane can be prepared by reacting an organic polyfunctional isocyanate with a suitable hydroxyl component, i.e., an organic compound having two or more reactive hydrogen atoms (as determined by the well-known Zerewitinoff determination) such as are found, for example, on a polyester, a polyester amide, a polyalkylene ether, a polyacetal or a polyalkylene thioether. When this reaction is conducted under anhydrous conditions, the resulting polyurethane may be non-porous.

If a cellular or foamed product is desired, water and at least an equivalent amount of isocyanate can be added to the mixture. When water reacts with the isocyanate groups not previously reacted, carbon dioxide is formed and is entrapped in the reaction mixture. An auxiliary blowing agent, such as a volatile fluorocarbon, may also be employed. The gelling time of the re- A action mixture is commonly controlled preferably to be slightly longer than the rise time, so that the solidifying mass entraps therewith the carbon dioxide or other gas thereby giving a foamed product.

In the manufacture of polyurethane foams, the ability to hold load carrying capacity constant at a constant density and in many cases the ability to achieve maximum load carrying capacity at a given density are both very important, especially from an economic standpoint and from a quality control standpoint. A way of increasing load carrying capacity is to increase the polyisocyanate content although this is not too efficient. Furthermore, in factory production the use of a higher isocyanate index increases the potential danger of fire in green (not completely cured) foam storage areas.

In accordance with this invention, there is prepared a polyurethane foam of improved physical and chemical properties such as increased load supporting capacity, increased tensile strength, increased modulus of elasticity, and increased solvent resistance.

SUMMARY OF THE INVENTION This invention comprises the preparation of a polyurethane of improved physical and chemical properties by the chemical reaction of A. an organic polyisocyanate and B. the copolymer of a. a polymerizable organic vinyl monomer having either one double bond or two double bonds in conjugation to each other and b. a hydroxyl-containing c-omonomer consisting essentially of an unsaturated polyalkylene ether macromonomer which has an equivalent weight per hydroxyl group of about to 3,000 and which contains one to three hydroxyl groups and one copolymerizable unsaturation per molecule.

In one embodiment of this invention, there is prepared a flexible or rigid polyurethane foam having improved strength and solvent resistance.

In another embodiment of this invention there is prepared a flexible polyurethane foam having improved load supporting ability and load deflection characteristics compared to conventionally prepared flexible foams of equal density.

In still another embodiment of this invention there is prepared a rigid polyurethane foam having improved strength per volume ratio.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the practice hereof it has been discovered that unique and valuable polyol resins can be obtained when vinyl monomers are copolymerized with a polyether containing one polymerizable carbon-carbon double bond and one to three hydroxyl groups per molecule.

The hydroxyl-carrying, unsaturated polyether (macromonomer) can be readily prepared by the homopolymerization or copolymerization of alkylene oxides of the general formula:

where R is hydrogen or an alkyl group of less than 10 carbon atoms and Q is an alkyl or aryl group of less than 10 carbon atoms or R'Cl-I where R is an aryl, alkoxy or alkyl carboxy group of less than 10 carbon atoms.

Typical alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and alkyl or aryl glycidyl ethers or esters polymerized with a catalyst, preferably a complex cyanide catalyst, e.g., Zn -,(Co(CN) in the presence of an appropriate unsaturated initiator. Such catalysts are shown in U.S. Pat. Nos. 3,427,256; 3,427,334; and 3,427,335.

The selected initiator is a compound containing one polymerizable unsaturated group and one to three active hydrogen atoms capable of initiating alkylene oxide polymerization in combination with the selected catalyst.

Examples of suitable initiators are: monobasic acids such as acrylic, methacrylic, crotonic, cinnamic and abietic acid and their hydroxy alkyl esters or amides; dibasic acids or their derivatives such as maleic, fumaric, citraconic, itaconic, mesaconic, chloromaleic, cyclohexene dicarboxylic, endomethylene cyclohexene dicarboxylic and chlorendic acid and their monoesters, monoamides and corresponding hydroxyalkyl derivatives; tribaslb acids such as aconitic aciid and its mono and diesters alld amides and corresponding hydroxylalkyl derivativ'fi hydroxyalkyl 9r dihydroxyl alkyl vinyl ethers or unsaturated hydrolfycarrying compounds such as allyl, cfQtyl and methallyl alcohol, butanediol and its homologues; monoallyl, crotyl or methallyl ethers of dihydroxy or trihydroxy alkanes; hydroxy alkyl N-vinyl carbamates or N-vinyl-N-hydroxy alkylurea and others.

The macromonomers obtained after addition of alkylene oxide to the initiator may have equivalent weights between 100 and 3,000 per hydroxyl group.

The vinyl compounds used in combination with the above macromonomer can be any monomer or monomer blend which can be made to copolymerize with the macromonomer by a radical-mechanism under utilization of any of the techniques known to the art.

Examples for these vinyl monomers are: acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidenechloride, the low molecular weight acrylates and methacrylates,acrylamide, styrene and substituted styrenes, itaconates, butadiene, isoprene, vinyl pyridines, vinyl sulfonates, vinyl and allyl derivatives of the phosphorus acids and many others.

The copolymen'zation can be carried out either in bulk, preferably in the presence of sufficient chain transfer agent to prevent the formation of higher than desired molecular weights, or in solution.

Either peroxides or aliphatic diazo compounds can be used as initiators for the radical polymerization. The molecular weight of the copolymer as determined by any colligative method will generally be in the neighborhood of 500 to 7,000 depending on the molecular weight of the macromonomer and the desired end product. Polymerization conditions (temperature, time, amount and type of chain transfer agent, etc.) will depend on the type of monomers utilized.

The copolymers are preferably viscous liquids (especially if they are to be used as the only polyol-component in urethane preparations without solvent) or solids which can be dissolved in commercial polyols or in solvents generally used in polyurethane coatings preparation. The charge ratio of macromonomer to vinyl monomer(s) (in moles) can be between 1:5 to 1:50 depending on the desired end product and the copolymerization 'behaviorof the monomers. The copolymerization is preferably conducted such that the average functionality of the obtained resins is between 2 and 4 (when the intended end use is in flexible urethanes) or higher (e.g., 3 to 6) when resins for rigid materials are desired.

The average functionality is generally determined by the ratio of vinyl monomer to hydroxy carrying component and the molecular weight of the copolymer.

The copolymer resins of this invention can be used in all types of polyurethanes such as coatings, adhesives,

" cast'elastomers, and rigid or flexible foams. They can 4 sulfone-4,4-diisocyanate, dichlorohexamethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, lchlorobenzene-2 ,4-diiso cyanate, 4,4 ,4 -triisocyanato triphenylmethane, 1,3,5-triisocyanato benzene, 2,4,6- triisocyanato toluene, 4,4'-dimethyl diphenylmethane- 2,2',5 ,5 -tetraisocyanate, furfurylidene diisocyanate and the like. Of the various polyisocyanates which can be used, the toluene diisocyanates are preferred, particularly an isomeric mixture of 2,4-toluene diisocyanate and 20% 2,6-toluene diisocyanate.

The following examples represent some of the best embodiments contemplated by the inventors in the practice of this invention. Unless otherwise stated, all quantitative measurements are by weight.

EXAMPLE I A. Preparation Of Unsaturated Polyether Glycol (Macromonomer) A polypropylene ether glycol was prepared according to the procedure described in US. Pat. No. 3,654,224.

1,500 grams (g) of propylene oxide, 2 g. of Zn (CoCN dimethoxy-ethane complex and 232 g. of maleic acid were charged to a closed reactor at 40F. The temperature was gradually raised to 170F. and stirring continued at this temperature until the original pressure within the reactor dropped to 5-l0 psi. At this point another 1,500 g. of propylene oxide was added over a time period of 2 hours and stirring continued for 3 more hours. The polyether glycol, after removal of volatile materials at 200F. in vacuo, had a hydroxyl number of 76.75 mg.KOH/g. corresponding to an average molecular weight of 1,460. Attempts to initiate propylene oxide polymerization with the potassium salt of maleic acid were unsuccessful.

B. Copolymerization with Vinyl Chloride 125 grams of the above polyether glycol, 25 g. of vinyl chloride, 0.5 g. azo-bisisobutyronitrile, ml. benzene and 10 ml. carbontetrachloride were charged to a polymerization bottle and rotated in a constant temperature bath at 80C. for 24 hours. Elimination of solvent and non-reacted monomer in a vacuum gave a homogeneous viscous, liquid with hydroxyl number 58.5 mg.KOH/g. and acid number 1.5 mg.KOH/g. corresponding to an average equivalent weight of 975.

C. Polyurethane Films Films were prepared from the original polyether and the copolymer according to the recipe:

0.01 gm.-equivalent polyetherpolyol based on hydroxyl 0.01 gm.-equivalent 1,2,4-butanetriol based on hydroxyl 0.2 gm. stannous octoate 0.02 gm. tn'ethylene diarnine (33 wt. in H O) 0.022 gm.-equivalent of an 80/20 mixture of 2,4- and 2,6- toluene diisocyanates (TDI) The films were cast on glass plates and cured for 1 hour at room temperature followed by 8 hours at C. in an air circulated oven. After cooling, the films were pulled off the glass plate and tested.

A saturated polypropylene ether succinate was obtained when succinic acid was substitued for maleic acid as the initiator for propylene-oxide polymerization. This glycol, when treated with vinyl chloride and radical initiator in the presence of chain transfer agent under conditions identical to [(13), gave only heterogeneous dispersions of polyvinyl chloride in the glycol.

Polyurethane films were prepared from these dispersions and TDI in a manner identical to the foregoing. The resulting films were extremely weak and brittle.

EXAMPLE II Original Vinyl Chloride Property Polyether Modified Polyether Mod. 100% (psi) 300 2254 Elong. 390 150 Tensile (psi) 540 3100 Tear (pli) 97 404 EXAMPLE III The polyether of Example 1(A) (100 g.) was copolymerized with methacrylonitrile (20 g.) at 80C. for 24 hours in the presence of azobisisobutyronitrile (0.4 g.) and 100 ml. ofa :90 blend of carbontetachloride and benzene. The resulting creamy white, viscous material had a hydroxyl number of 57.8 mg. KOH/g. and an acid number of 0.79 mg.KOII/g.

A film prepared from this polyol according to the procedure and recipe given in Example I(C) had modulus (at 100% elong.) of 303 psi, a tensile strength of 1,490 psi, an elongation of 183% and a tear strength of 127 pli.

EXAMPLE IV A. A polypropylene ether glycol containing one itaconateunit per mole of polyether was prepared as in Example I by reacting itaconic acid (130 g.), propylene oxide (1870 g.) and zinc cobalticyanide (1.0 g.) in tet rahydrofuran (1000 g.) for 12 hours at 50C. The resulting viscous liquid had a hydroxyl number of 55.8 mg.KOH/g. corresponding to a glycol of molecular weight 2000.

B. Copolymerization with Acrylonitrile 120 grams of the above polyether, 30 g. of acrylonitrile, 0.3 g. azobisisobutyronitrile and 1.5 g. trichlorobromemethane were charged to a polymerization bottle. The bottle was sealed and placed in an 80C. constant temperature bath for 24 hours.

After removal of volatiles at 70C under reduced pressure there remained 140 g. of an orange-colored,

clear, viscous liquid which had the following properties:

Brookfield viscosity 25.000 cps.

Hydroxyl number 506 mg.KOH/g; EW 1100 Molecular weight (VPO) 4590 Functionality 4.1

Nitrogen 3.78%

C. Flexible Urethane Foam Preparation and Proper ties l-Iandmixed, one-shot flexible foams were prepared from blends of the above copolymer-polyol IV(B) with a standard, commercially available polypropylene ether triol having a number average molecular weight of about 3,000 (Poly G-3030 PG, Olin Mathieson). Formulations and load-bearing properties of the obtained foams are given in the following table.

FLEXIBLE URETHANE FOAMS PREPARED FROM THE EXPERI- MENTAL POLYOL OF EXAMPLE IV AND COMMER'CIALLY AVAILABLE POLYOLS A B C Poly G-3030 PG 100 50 Copolymer-Polyol 25 50 /20 TDI NCO Index 52. 54 54 Activator I" 4.6 4.6 4.6 Stannous octoate level varied to balance foam formulation Silicone surfactant 1.0 1.0 1.0 Diglycidyl ether of bisphenol A (Epon 828) 2 4 Density pcf 1.55 1.65 1.67 Compression load 4 X 4 X 2"sample Deflection. 25% 6.8 9.1 11.2 65% 12.9 18.5 23.9 Load factor 1.89 2.03 2.13

Tetramethylbutane diamine (0.05 g), N-methyl morpholine (0.6 3.), water (4.0 8).

EXAMPLE V A polyether containing an average of one maleate unit per molecule was prepared by esterification of polypropylene ether glycol of an average molecular weight 425 (2moles) with maleic anhydride (lmole). The resulting diol 80 gm.) was copolymerized with vinyl chloride (20 gm.) in the presence of 200 ml. of CCL, as chain transfer agent. Only partially crosslinked, soft gels were obtained. This Example shows that a conventional thermal polycondensation technique does not yield satisfactory starting materials (macromonomers) useful within the scope of this invention.

EXAMPLE VI Eighty grams of polypropylene ether glycol of average molecular weight M -l9l0 hydroxyl number 58.6 mg.I(OI-I/g.; viscosity 1,500 cps. at 20C. containing one itaconate unit per polyether molecule and prepared under the conditions and with the catalyst system 1 described in Example IV(A) was copolymerized with 20 grams of acrylonitrile at 50C. for 24 hours in the presence of triethylamine (1.06 g.) as chain transfer agent (initiator 0.2 g. azo-bisis-obutyronitrile).

After addition of antioxidant (0.1 g. di-2,6-tertiary butylphenol) and removal of volatile materials there 7 was obtained 90 g. of a viscous (29,000 cps at 20C.) homogeneous yellow liquid with the following properties:

H No. 51.3 mg.KOH/g.

Acid No. 013 mg.KOH/g.

acrylonitrile content 12.2% (calculated from N) M (VPO) 3200 Average functionality 2.9 (calculated) After 24 hours at 60C. a clear, semi-solid was obtained which was soluble in toluene and had a hydroxyl number of 29.7 mgKOl-l/g.

A moisture-cured polyurethane film made from this polyol (one equivalent) and TDI (two equivalents) had tensile strength 3,500 psi; elongation 50%; Graves tear 497 pli, and a yield point at 4,500 psi.

We claim:

1. A method for the preparation of a liquid copolymer having an average functionality of 2 to 6 and selected from the class consisting of a copolymer of a vinyl monomer selected from styrene, methacrylonitrile, acrylonitrile and a lower alkyl acrylate or methacrylate with a polyalkylene ether itaconate macromonomer having an equivalent weight of about 100 to 3,000 per hydroxyl group, having one to three hydroxyl groups per itaconate PPG- Polyol Poly G-3030 PG itaconate PPG AN Copolymer QH No. 56 58.6 51.3

M,, 3.000 1,910 3,200 (VPO) (end groups) (end groups) Functionality 2.7 2 2.9

NCO/OH Ratio 2 2 2 Mod. at 50% 343 490 900 elong. (psi) Tensile strength 570 790 1,250

at break (psi) Linear swell 45 40 27 in toluene after 24 hrs. immersion EXAMPLE V" molecule, and havln g one copolymenzable carbon- A. Propylene oxide was polymerized in the presence of itaconic acid and Zn (Co(CN) as described in Example l. The obtained glycol had a hydroxyl number of 76 mg.KOH/g. corresponding to an average molecular weight of 1,470.

B. Forty grams of this polypropylene ether itaconate were copolymerized with 60 g. of styrene in 100 ml. carbontetrachloride using 0.6 g. of azo-bisisobutyronitrile as initiator for 24 hours at 60C. Removal of the solvent in vacuo gave a low melting soft solid with a hydroxyl number of 32.8 mg.KOl-l/g.

C. Moisture-cured polyurethane films were made from the original polypropylene ether itaconate 7(A) as well as the styrene-modified polyol Vll(B) and TDl (NCO/OH 2.2) and tested. The following properties resulted:

A film made from a physical blend of polystyrene of similar molecular weight with polypropylene ether itaconate and TDl under the same conditions gave only a very weak, heterogeneous film.

EXAMPLE VIII The polypropylene ether itaconate prepared in the Example V11 (40 g.) was copolymerized with 60 g. of methylmethacrylate in 100 ml. of benzene using 0.6 g. azo-bisisobutyronitrile as the initiator. 1 i

to-carbon double bond per molecule; and a copolymer of a vinyl monomer selected from vinyl chloride, vinylidene chloride and vinyl acetate with a polyalkylene ether maleate or fumarate macromonomer having an equivalent weight of about 100 to 3,000 per hydroxyl group, having one to three hydroxyl groups per molecule, and having one copolymerizable carbon-to-carbon double bond per molecule, said method consisting essentially of 1. mixing the macromonomer and the vinyl monomer in a mole ratio of 1:5 to 1:50 simultaneously with a chain transfer agent and an initiator for radical polymerization, said initiator being selected from peroxides and aliphatic diazo compounds; and 2. activating said initiator to cause the copolymerization of said copoylmer components. 2. A method in accordance with claim 1 wherein said macromonomers contain no more than two hydroxyl groups per molecule.

3. A copolymer prepared in accordance with the method of claim 1, said copolymer having a molecular weight ranging from about 500 to 7,000.

4. A copolymer in accordance with claim 3 wherein said copolymer is liquid at ambient temperatures.

5. A copolymer in accordance with claim 3 wherein said vinyl monomer is styrene.

6. A copolymer in accordance with claim 3 wherein said vinyl monomer is acrylonitrile.

7. A copolymer in accordance with claim 3 wherein said vinyl monomer is methyl methacrylate.

8. A copolymer in accordance with claim 3 wherein said vinyl monomer is vinyl chloride and said mac- 

1. A METHOD FOR THE PREPARATION OF A LIQUID COPOLYMER HAVING AN AVERAGE FUNCTIONALITY OF 2 TO 6 AND SELECTED FROM THE CLASS CONSISTING OF A COPOLYMER OF A VINYL MONOMER SELECTED FROM STYRENE, METACRYLONITRILE, ACRYLONITRILE AND A LOWER ALKYL ACRYLATE OR METHACRYLATE WITH A POLYALKYLENE ETHERITACONATE MACROMONOMER HAVING AN EQUIVALENT WEIGHT OF ABOUT 100 TO 3,000 PER HYDROXYL GROUP, HAVING ONE COPOLYMERIZABLE GROUPS PER MOLECULE, AND HAVING ONE COPOLYMERIZABLE CARBON-TO CARBON DOUBLE BOND PER MOLECULE, AND A COPOLYMER OF A VINYL MONOMER SELECTED FROM VINYL CHLORIDE, VINYLIDENE CHLORIDE AND VINYL ACETATE WITH A POLYALKYLENE ETHER MALEATE OR FUMARATE MACROMONOMER HAVING AN EQUIVALENT WEIGHT OF ABOUT 100 TO 3,000 PERHYDROXYL GROUP, HAVING ONE TO TREE HYDROXYL GROUPS PER MOLECULE, AND HAVING ONE COPOLYMERIZABLE CARBON-TO-CARBON DOUBLE BOND PER MOLECULE, SAID METHOD CONSISTING ESSENTIALLY OF
 1. MIXING THE MACROMONOMER AND THE VINYL MONOMER IN A MOLE RATIO OF 1:5 TO 1:50 SIMULTANEOUSLY WITH A CHAIN TRANSFER AGENT AN AN INITIATOR FOR RADICAL POLYMERIZATION, SAID INITIATOR BEING SELCTED FROM PEROXIDES AND ALIPHATIC DIAZO COMPOUNDS, AND
 2. ACTIVATING SAID INITIATOR TO CAUSE THE COPOLYMERIZATION OF SAID COPOLYMR COMPONENTS.
 2. activating said initiator to cause the copolymerization of said copoylmer components.
 2. A method in accordance with claim 1 wherein said macromonomers contain no more than two hydroxyl groups per molecule.
 3. A copolymer prepared in accordance with the method of claim 1, said copolymer having a molecular weight ranging from about 500 to 7,000.
 4. A copolymer in accordance with claim 3 wherein said copolymer is liquid at ambient temperatures.
 5. A copolymer in accordance with claim 3 wherein said vinyl monomer is styrene.
 6. A copolymer in accordance with claim 3 wherein said vinyl monomer is acrylonitrile.
 7. A copolymer in accordance with claim 3 wherein said vinyl monomer is methyl methacrylate.
 8. A copolymer in accordance with claim 3 wherein said vinyl monomer is vinyl chloride and said macromonomer is a polyalkylene ether maleate. 